EP2168680A1 - Catalyst composition and method for producing cross-coupling compound using the same - Google Patents
Catalyst composition and method for producing cross-coupling compound using the same Download PDFInfo
- Publication number
- EP2168680A1 EP2168680A1 EP08790988A EP08790988A EP2168680A1 EP 2168680 A1 EP2168680 A1 EP 2168680A1 EP 08790988 A EP08790988 A EP 08790988A EP 08790988 A EP08790988 A EP 08790988A EP 2168680 A1 EP2168680 A1 EP 2168680A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- substituted
- unsubstituted
- nickel
- catalyst composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 239000000203 mixture Substances 0.000 title claims abstract description 79
- 150000001875 compounds Chemical class 0.000 title claims abstract description 66
- 238000006880 cross-coupling reaction Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title description 4
- -1 nitrogen-containing heterocyclic compound Chemical class 0.000 claims abstract description 114
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 125000003118 aryl group Chemical group 0.000 claims abstract description 36
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 32
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 29
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 27
- 125000006165 cyclic alkyl group Chemical group 0.000 claims abstract description 26
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 24
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 21
- 125000005843 halogen group Chemical group 0.000 claims abstract description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011737 fluorine Substances 0.000 claims abstract description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 15
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-M methanesulfonate group Chemical group CS(=O)(=O)[O-] AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 claims abstract description 5
- LBLYYCQCTBFVLH-UHFFFAOYSA-M toluenesulfonate group Chemical group C=1(C(=CC=CC1)S(=O)(=O)[O-])C LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 36
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 9
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 7
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 229910001507 metal halide Inorganic materials 0.000 claims description 4
- 150000005309 metal halides Chemical class 0.000 claims description 4
- 150000002901 organomagnesium compounds Chemical class 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 125000004429 atom Chemical group 0.000 abstract 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical group [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 abstract 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 47
- 239000004615 ingredient Substances 0.000 description 23
- 229910021587 Nickel(II) fluoride Inorganic materials 0.000 description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 12
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 150000004820 halides Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 9
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical group C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 238000005859 coupling reaction Methods 0.000 description 8
- 125000004093 cyano group Chemical group *C#N 0.000 description 8
- 125000004185 ester group Chemical group 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 150000002815 nickel Chemical class 0.000 description 5
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 5
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- BVUQKCCKUOSAEV-UHFFFAOYSA-M magnesium;methylbenzene;bromide Chemical compound [Mg+2].[Br-].CC1=CC=[C-]C=C1 BVUQKCCKUOSAEV-UHFFFAOYSA-M 0.000 description 4
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 4
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 4
- 125000003367 polycyclic group Chemical group 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- XZDYFCGKKKSOEY-UHFFFAOYSA-N 1,3-bis[2,6-di(propan-2-yl)phenyl]-4,5-dihydro-2h-imidazol-1-ium-2-ide Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N1CCN(C=2C(=CC=CC=2C(C)C)C(C)C)[C]1 XZDYFCGKKKSOEY-UHFFFAOYSA-N 0.000 description 3
- AVJBQMXODCVJCJ-UHFFFAOYSA-M 1,3-bis[2,6-di(propan-2-yl)phenyl]imidazol-1-ium;chloride Chemical compound [Cl-].CC(C)C1=CC=CC(C(C)C)=C1N1C=[N+](C=2C(=CC=CC=2C(C)C)C(C)C)C=C1 AVJBQMXODCVJCJ-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 3
- 229910021582 Cobalt(II) fluoride Inorganic materials 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 3
- ZBQUMMFUJLOTQC-UHFFFAOYSA-N dichloronickel;3-diphenylphosphaniumylpropyl(diphenyl)phosphanium Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1[PH+](C=1C=CC=CC=1)CCC[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 ZBQUMMFUJLOTQC-UHFFFAOYSA-N 0.000 description 3
- BOUYBUIVMHNXQB-UHFFFAOYSA-N dicyclohexyl(2-dicyclohexylphosphanylethyl)phosphane Chemical compound C1CCCCC1P(C1CCCCC1)CCP(C1CCCCC1)C1CCCCC1 BOUYBUIVMHNXQB-UHFFFAOYSA-N 0.000 description 3
- RSJBEKXKEUQLER-UHFFFAOYSA-N dicyclohexyl(3-dicyclohexylphosphanylpropyl)phosphane Chemical compound C1CCCCC1P(C1CCCCC1)CCCP(C1CCCCC1)C1CCCCC1 RSJBEKXKEUQLER-UHFFFAOYSA-N 0.000 description 3
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 3
- MWVXFEZPEPOQRE-UHFFFAOYSA-N ditert-butyl(2-ditert-butylphosphanylethyl)phosphane Chemical compound CC(C)(C)P(C(C)(C)C)CCP(C(C)(C)C)C(C)(C)C MWVXFEZPEPOQRE-UHFFFAOYSA-N 0.000 description 3
- FJILYPCZXWVDMD-UHFFFAOYSA-N ditert-butyl(3-ditert-butylphosphanylpropyl)phosphane Chemical compound CC(C)(C)P(C(C)(C)C)CCCP(C(C)(C)C)C(C)(C)C FJILYPCZXWVDMD-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 3
- VGZIOHINNQGTOU-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VGZIOHINNQGTOU-UHFFFAOYSA-N 0.000 description 3
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 235000009518 sodium iodide Nutrition 0.000 description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 3
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 3
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 3
- 229940102001 zinc bromide Drugs 0.000 description 3
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 2
- JHLKSIOJYMGSMB-UHFFFAOYSA-N 1-bromo-3,5-difluorobenzene Chemical compound FC1=CC(F)=CC(Br)=C1 JHLKSIOJYMGSMB-UHFFFAOYSA-N 0.000 description 2
- UAXNXOMKCGKNCI-UHFFFAOYSA-N 1-diphenylphosphanylethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 UAXNXOMKCGKNCI-UHFFFAOYSA-N 0.000 description 2
- LRLQQERNMXHASR-UHFFFAOYSA-N 2-diphenylphosphanylpropan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 LRLQQERNMXHASR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910004039 HBF4 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 2
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003828 azulenyl group Chemical group 0.000 description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000004090 cyclononenyl group Chemical group C1(=CCCCCCCC1)* 0.000 description 2
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 2
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- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
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- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 125000005956 isoquinolyl group Chemical group 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- RBWRWAUAVRMBAC-UHFFFAOYSA-M magnesium;methoxybenzene;bromide Chemical compound [Mg+2].[Br-].COC1=CC=[C-]C=C1 RBWRWAUAVRMBAC-UHFFFAOYSA-M 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 2
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- YOCBOYPGZVFUCQ-UHFFFAOYSA-L nickel(2+);tricyclohexylphosphane;dichloride Chemical compound Cl[Ni]Cl.C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 YOCBOYPGZVFUCQ-UHFFFAOYSA-L 0.000 description 2
- QEKXARSPUFVXIX-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dibromide Chemical compound [Ni+2].[Br-].[Br-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QEKXARSPUFVXIX-UHFFFAOYSA-L 0.000 description 2
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Ni+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 description 2
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- UYLRKRLDQUXYKB-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UYLRKRLDQUXYKB-UHFFFAOYSA-N 0.000 description 2
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- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
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- 238000000746 purification Methods 0.000 description 2
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- 230000009257 reactivity Effects 0.000 description 2
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- WKALCYAZQNVDNE-UHFFFAOYSA-N triethoxy phosphite Chemical compound CCOOP(OOCC)OOCC WKALCYAZQNVDNE-UHFFFAOYSA-N 0.000 description 2
- WCQYHKQWAYQAPR-UHFFFAOYSA-N trimethoxy phosphite Chemical compound COOP(OOC)OOC WCQYHKQWAYQAPR-UHFFFAOYSA-N 0.000 description 2
- HUYTYZKCRIGZCC-UHFFFAOYSA-N triphenoxy phosphite Chemical compound C=1C=CC=CC=1OOP(OOC=1C=CC=CC=1)OOC1=CC=CC=C1 HUYTYZKCRIGZCC-UHFFFAOYSA-N 0.000 description 2
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- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 229920002554 vinyl polymer Polymers 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
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- BHIJGQUZXXURRH-ODZAUARKSA-N (z)-but-2-enedioic acid;nickel Chemical compound [Ni].OC(=O)\C=C/C(O)=O BHIJGQUZXXURRH-ODZAUARKSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- NREOZXRFNFCTHM-UHFFFAOYSA-N 1,3-bis[2,6-di(propan-2-yl)phenyl]imidazolidin-1-ium;chloride Chemical compound [Cl-].CC(C)C1=CC=CC(C(C)C)=C1N1C[NH+](C=2C(=CC=CC=2C(C)C)C(C)C)CC1 NREOZXRFNFCTHM-UHFFFAOYSA-N 0.000 description 1
- UFNFKGALOVQDLX-UHFFFAOYSA-N 1,3-difluoro-5-(4-methoxyphenyl)benzene Chemical group C1=CC(OC)=CC=C1C1=CC(F)=CC(F)=C1 UFNFKGALOVQDLX-UHFFFAOYSA-N 0.000 description 1
- KPYDTUDJJROKRT-UHFFFAOYSA-N 1,3-ditert-butyl-2-(1,3-ditert-butylimidazolidin-2-ylidene)-1H-imidazol-1-ium chloride Chemical compound [Cl-].CC(C)(C)N1CCN(C(C)(C)C)C1=C1[NH+](C(C)(C)C)C=CN1C(C)(C)C KPYDTUDJJROKRT-UHFFFAOYSA-N 0.000 description 1
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- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RMSOEGBYNWXXBG-UHFFFAOYSA-N 1-chloronaphthalen-2-ol Chemical compound C1=CC=CC2=C(Cl)C(O)=CC=C21 RMSOEGBYNWXXBG-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- CDGJQIHCYSGEFH-UHFFFAOYSA-N 2-[1,3-bis[2,6-di(propan-2-yl)phenyl]imidazolidin-2-ylidene]-1,3-bis[2,6-di(propan-2-yl)phenyl]-1H-imidazol-1-ium chloride Chemical compound [Cl-].CC(C)C1=CC=CC(C(C)C)=C1N(CCN1C=2C(=CC=CC=2C(C)C)C(C)C)C1=C1[NH+](C=2C(=CC=CC=2C(C)C)C(C)C)C=CN1C1=C(C(C)C)C=CC=C1C(C)C CDGJQIHCYSGEFH-UHFFFAOYSA-N 0.000 description 1
- IPBBPIKNVOONQZ-UHFFFAOYSA-L 2-hydroxypropanoate;nickel(2+) Chemical compound [Ni+2].CC(O)C([O-])=O.CC(O)C([O-])=O IPBBPIKNVOONQZ-UHFFFAOYSA-L 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910017048 AsF6 Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- 229910021584 Cobalt(II) iodide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 229910021579 Iron(II) iodide Inorganic materials 0.000 description 1
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- 229910014332 N(SO2CF3)2 Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- MTMGAPZENLSQDH-UHFFFAOYSA-N [Cl-].CC1=CC(C)=CC(C)=C1N(C=CN1C=2C(=CC(C)=CC=2C)C)C1=C1N(C(C)(C)C)C[NH+](C(C)(C)C)C1 Chemical compound [Cl-].CC1=CC(C)=CC(C)=C1N(C=CN1C=2C(=CC(C)=CC=2C)C)C1=C1N(C(C)(C)C)C[NH+](C(C)(C)C)C1 MTMGAPZENLSQDH-UHFFFAOYSA-N 0.000 description 1
- BJHJOCXRDSJKTR-UHFFFAOYSA-N [Cl-].CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=C1[NH+](C=2C(=CC(C)=CC=2C)C)C=CN1C1=C(C)C=C(C)C=C1C Chemical compound [Cl-].CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=C1[NH+](C=2C(=CC(C)=CC=2C)C)C=CN1C1=C(C)C=C(C)C=C1C BJHJOCXRDSJKTR-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940070337 ammonium silicofluoride Drugs 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- JZKFIPKXQBZXMW-UHFFFAOYSA-L beryllium difluoride Chemical compound F[Be]F JZKFIPKXQBZXMW-UHFFFAOYSA-L 0.000 description 1
- 229910001633 beryllium fluoride Inorganic materials 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- LVEULQCPJDDSLD-UHFFFAOYSA-L cadmium fluoride Chemical compound F[Cd]F LVEULQCPJDDSLD-UHFFFAOYSA-L 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- SLFKPACCQUVAPG-UHFFFAOYSA-N carbon monoxide;nickel;triphenylphosphane Chemical compound O=C=[Ni]=C=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 SLFKPACCQUVAPG-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- GAYAMOAYBXKUII-UHFFFAOYSA-L cobalt(2+);dibenzoate Chemical compound [Co+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAYAMOAYBXKUII-UHFFFAOYSA-L 0.000 description 1
- FJNQKAYLLNDYTJ-UHFFFAOYSA-N cobalt(2+);diborate Chemical compound [Co+2].[Co+2].[Co+2].[O-]B([O-])[O-].[O-]B([O-])[O-] FJNQKAYLLNDYTJ-UHFFFAOYSA-N 0.000 description 1
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- ZUKDFIXDKRLHRB-UHFFFAOYSA-K cobalt(3+);triacetate Chemical compound [Co+3].CC([O-])=O.CC([O-])=O.CC([O-])=O ZUKDFIXDKRLHRB-UHFFFAOYSA-K 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- 229910000335 cobalt(II) sulfate Inorganic materials 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 description 1
- JUPWRUDTZGBNEX-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O JUPWRUDTZGBNEX-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- ZOLLIQAKMYWTBR-RYMQXAEESA-N cyclododecatriene Chemical compound C/1C\C=C\CC\C=C/CC\C=C\1 ZOLLIQAKMYWTBR-RYMQXAEESA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- XXECWTBMGGXMKP-UHFFFAOYSA-L dichloronickel;2-diphenylphosphanylethyl(diphenyl)phosphane Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 XXECWTBMGGXMKP-UHFFFAOYSA-L 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- AKXNPPNNEDIAJL-UHFFFAOYSA-N diiodonickel;triphenylphosphanium Chemical compound I[Ni]I.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 AKXNPPNNEDIAJL-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- QHEDSQMUHIMDOL-UHFFFAOYSA-J hafnium(4+);tetrafluoride Chemical compound F[Hf](F)(F)F QHEDSQMUHIMDOL-UHFFFAOYSA-J 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 1
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GHDIHPNJQVDFBL-UHFFFAOYSA-N methoxycyclohexane Chemical compound COC1CCCCC1 GHDIHPNJQVDFBL-UHFFFAOYSA-N 0.000 description 1
- LNDHQUDDOUZKQV-UHFFFAOYSA-J molybdenum tetrafluoride Chemical compound F[Mo](F)(F)F LNDHQUDDOUZKQV-UHFFFAOYSA-J 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- GAIQJSWQJOZOMI-UHFFFAOYSA-L nickel(2+);dibenzoate Chemical compound [Ni+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAIQJSWQJOZOMI-UHFFFAOYSA-L 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- ZLQBNKOPBDZKDP-UHFFFAOYSA-L nickel(2+);diperchlorate Chemical compound [Ni+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZLQBNKOPBDZKDP-UHFFFAOYSA-L 0.000 description 1
- JMWUYEFBFUCSAK-UHFFFAOYSA-L nickel(2+);octadecanoate Chemical compound [Ni+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JMWUYEFBFUCSAK-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KFBKRCXOTTUAFS-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 KFBKRCXOTTUAFS-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- MLKFZZUUYQWFMO-UHFFFAOYSA-H osmium hexafluoride Chemical compound F[Os](F)(F)(F)(F)F MLKFZZUUYQWFMO-UHFFFAOYSA-H 0.000 description 1
- BHZSLLSDZFAPFH-UHFFFAOYSA-L palladium(2+);difluoride Chemical compound F[Pd]F BHZSLLSDZFAPFH-UHFFFAOYSA-L 0.000 description 1
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 1
- NFVUDQKTAWONMJ-UHFFFAOYSA-I pentafluorovanadium Chemical compound [F-].[F-].[F-].[F-].[F-].[V+5] NFVUDQKTAWONMJ-UHFFFAOYSA-I 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- SQTLECAKIMBJGK-UHFFFAOYSA-I potassium;titanium(4+);pentafluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[K+].[Ti+4] SQTLECAKIMBJGK-UHFFFAOYSA-I 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- GRJJQCWNZGRKAU-UHFFFAOYSA-N pyridin-1-ium;fluoride Chemical compound F.C1=CC=NC=C1 GRJJQCWNZGRKAU-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- OJIKOZJGHCVMDC-UHFFFAOYSA-K samarium(iii) fluoride Chemical compound F[Sm](F)F OJIKOZJGHCVMDC-UHFFFAOYSA-K 0.000 description 1
- OEKDNFRQVZLFBZ-UHFFFAOYSA-K scandium fluoride Chemical compound F[Sc](F)F OEKDNFRQVZLFBZ-UHFFFAOYSA-K 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- CULOEOTWMUCRSJ-UHFFFAOYSA-M thallium(i) fluoride Chemical compound [Tl]F CULOEOTWMUCRSJ-UHFFFAOYSA-M 0.000 description 1
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- VNCUSYIKPZQFST-UHFFFAOYSA-K trifluoroiridium Chemical compound F[Ir](F)F VNCUSYIKPZQFST-UHFFFAOYSA-K 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- TXUZMGFRPPRPQA-UHFFFAOYSA-K trifluororhodium Chemical compound F[Rh](F)F TXUZMGFRPPRPQA-UHFFFAOYSA-K 0.000 description 1
- YRQNNUGOBNRKKW-UHFFFAOYSA-K trifluororuthenium Chemical compound F[Ru](F)F YRQNNUGOBNRKKW-UHFFFAOYSA-K 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- NEHOZOUEOAZNQN-UHFFFAOYSA-N triphenyl(4-triphenylphosphaniumylbutyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CCCC[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 NEHOZOUEOAZNQN-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229940105963 yttrium fluoride Drugs 0.000 description 1
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
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Definitions
- This invention relates to a catalyst composition exhibiting a high catalytic activity and selectivity for a cross-coupling reaction in organic syntheses, and a process for producing a coupled compound using the catalyst composition.
- Various functional compounds can be produced with an enhanced efficiency by the process according to the present invention. More specifically, unsymmetrical biaryl compounds and other compounds which are useful, for example, as liquid crystal or a raw material for medicines can be produced with an enhanced efficiency.
- Unsymmetrical biaryl compounds characterized as having stability due to their aromatic rings and fixed molecular structure are very useful as electronic materials, and intermediates for the synthesis of medicines and pesticides, and various functional compounds.
- Unsymmetrical biaryl compounds have heretofore been produced widely by a process comprising cross-coupling an organic halide with an organometallic compound in the presence of a catalyst.
- a nickel catalyst or a palladium catalyst are usually used as a catalyst.
- these processes have problems. That is, in the case when a nickel catalyst is used, homo-coupled compounds derived from an organometallic compound or an organic halide are produced in large amounts by side reactions. Purification of the thus-synthesized unsymmetrical biaryl compounds required for use as liquid crystal and intermediate for medicines is very costly. In the case when a palladium catalyst is used, the catalyst is expensive and the process is costly and industrially not advantageous.
- An object of the present invention is to provide a catalyst composition exhibiting high activity and selectivity for the cross-coupling reaction for which an industrially satisfying process has not been heretofore proposed, especially a catalyst which does not produce homo-coupled compounds by side reactions from an organometallic compound or an organic halide.
- Another object of the present invention is to provide a process for producing a cross-coupled compound using the above-mentioned catalyst composition.
- a novel catalyst composition comprising a nickel metal source, a fluorine source and a nitrogen-containing heterocyclic compound having a specific structure, or a phosphine compound exhibits very high activity and selectivity for the cross-coupling reaction of an organometallic compound such as an organomagnesium compound or a organozinc compound with an organic halide, and said catalyst does not cause the problem of producing homo-coupled compounds by side reactions.
- a catalyst composition for a cross-coupling reaction comprising a nickel metal source, a fluorine source, and a nitrogen-containing heterocyclic compound represented by the following formula (1A) or (1B), or a phosphine compound:
- R 1 and R 2 may be the same or different and represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkyl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group
- R 3 and R 4 may be the same or different and represent a hydrogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted silyl group
- - - - - - - - - - - represents a single bond or a double bond
- X - represents a univalent anion
- R 5 -R 6 a process for producing a cross-coupled compound represented by the following general formula (5): R 5 -R 6 (5) wherein R 5 and R 6 represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkyl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group,
- R 6 is the same as defined above, and Y 2 represents a halogen atom, a methanesulfonate group, a toluenesulfonate group or a trifluoromethanesulfonate group, in the presence of at least one catalyst composition as mentioned above.
- the catalyst composition according to the present invention is a novel catalyst composition, which has not heretofore been proposed, and exhibits high activity and selectivity for a cross-coupling reaction. That is, this catalyst composition suppresses to a great extent the production of undesirable homo-coupled compounds by side reactions, to give the desired cross-coupled compound with a very high selectivity.
- the cross-coupling reaction for which an industrially satisfying process has not heretofore been proposed, can be industrially advantageously conducted.
- unsymmetrical biaryl compounds and other compounds which are useful as liquid crystal or a raw material for medicines can be produced with enhanced yield and selectivity.
- the catalyst composition according to the present invention does not contain an expensive metal such as palladium, therefore the coupling reaction using the catalyst composition is advantageous from an economical and industrial viewpoint.
- the catalyst composition of the present invention is classified into two types.
- a first type of the catalyst composition comprises a nickel metal source, a fluorine source and a nitrogen-containing heterocyclic compound of the following general formula (1A) or (1B):
- R 1 and R 2 may be the same or different and represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkyl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group.
- R 3 and R 4 may be the same or different and represent a hydrogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted silyl group.
- R 3 and R 4 may be bonded together to form a ring with the carbon atoms to which R 3 and R 4 are bonded.
- nitrogen-containing heterocyclic compound represented by the formula (1A) or (1B)
- first catalyst composition the first type catalyst composition containing this nitrogen-containing heterocyclic compound according to the present invention
- the nickel metal source which is one essential ingredient of the first catalyst composition, is capable of giving a nickel metal to a catalyst system.
- the nickel source is not particularly limited, and is usually selected from nickel salts with a valency of 0 to 2, and complex compounds derived from the nickel salts.
- nickel(0) powder there can be mentioned nickel(0) powder; nickel halides such as nickel(II) fluoride, nickel(II) chloride, nickel(II) bromide and nickel(II) iodide; inorganic nickel salts such as nickel(II) sulfate, nickel (II) nitrate, nickel (II) perchlorate and nickel (II) sulfide; and organic acid nickel salts such as nickel(II) formate, nickel(II) oxalate, nickel(II) acetate, nickel(II) fumarate, nickel(II) lactate, nickel(II) gluconate, nickel(II) benzoate, nickel (II) stearate, nickel (II) sulfamate, nickel (II) amidosulfate, nickel(II) carbonate and nickel(II) acetylacetonate.
- nickel halides such as nickel(II) fluoride, nickel(II) chlor
- the complex compounds derived from the nickel salts are not particularly limited, but usually include those which are represented by the following general formula (7): LcNiXd (7) wherein L represents a phosphine ligand, an amine ligand or a carbonyl ligand, and, when L is plural, they may be the same or different. These ligands may be crosslinked.
- c represents an integer in the range of 0 to 6.
- Ni has a valency of 0 to 2.
- X represents a halogen atom, a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and, when X is plural, they may be the same or different.
- d represents a number equal to the number for valency of Ni.
- Ni complex compound there can be mentioned bis(1,5-cyclooctadiene)nickel(0), bis(allyl)nickel(0), tetracarbonylnickel(0), tricarbonyl(triphenylphosphine)nickel(0), dicarbonylbis(triphenylphosphine)nickel(0), tetrakis(triphenylphosphine)nickel(0), bis[bis(tricyclohexylphosphine)nickel(0) dinitride, (ethylene)bis(triphenylphosphine)nickel(0), (cyclododecatriene)nickel(0), tris(triphenylphosphine)nickel(I) chloride, tris(triphenylphosphine)nickel(I) bromide, tris(triphenylphosphine)nickel(I) iodide, bis(triphenylphosphine)nickel(II) dichloride, bis(triphenyl
- the fluorine source which is one essential ingredient of the first catalyst composition, is capable of giving a fluorine atom to a catalyst system.
- the fluorine source is not particularly limited, and, as specific examples thereof, there can be mentioned fluorine gas, hydrofluoric acid, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, beryllium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, scandium fluoride, yttrium fluoride, lanthanum fluoride, titanium fluoride, zirconium fluoride, hafnium fluoride, vanadium fluoride, niobium fluoride, tantalum fluoride, chromium fluoride, molybdenum fluoride, tungsten fluoride, manganese fluoride, ruthenium fluoride, osmium fluoride, rhodium fluoride, iridium
- Nickel fluoride is capable of giving a nickel metal and simultaneously a fluorine atom to the catalyst system, therefore, nickel fluoride can be used alone as the nickel metal source and the fluorine source. Nickel fluoride is especially preferable in view of low cost, high reactivity and high stability.
- the first catalyst composition comprises, in addition to the above-mentioned nickel metal source and fluorine source, a nitrogen-containing heterocyclic compound of the following general formula (1A) or (1B) as an essential ingredient.
- a substituted or unsubstituted aryl group for R 1 , R 2 , R 3 and R 4 is not particularly limited, and includes, for example, substituted or unsubstituted aryl groups having 1 to 4 rings and 6 to 18 carbon atoms.
- the aryl groups there can be mentioned phenyl, naphthyl, anthracenyl, azulenyl, pyrenyl, phenanthrenyl and fluorenyl groups.
- Optional number of hydrogen atoms in these aryl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group, an ester group and an silyl group.
- substituents include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubsti
- a substituted or unsubstituted heteroaryl group for R 1 , R 2 , R 3 and R 4 is not particularly limited, and includes, for example, substituted or unsubstituted heteroaryl groups having 1 to 4 rings and 6 to 18 carbon atoms.
- the heteroaryl groups there can be mentioned pyridyl, pyrimidyl, pyridazyl, pyrazyl, triazyl, benzofuranyl, indolyl, benzothiofenyl, quinolyl, isoquinolyl, carbazolyl, acridinyl, phenanthrolinyl and phenothiazinyl groups.
- Optional number of hydrogen atoms in these heteroaryl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group and an ester group.
- substituents include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner,
- a substituted or unsubstituted linear, branched or cyclic alkyl group for R 1 , R 2 , R 3 and R 4 is not particularly limited, and includes, for example, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms.
- alkyl groups there can be mentioned methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclotetradecyl
- the substituted or unsubstituted alkyl group includes polycyclic hydrocarbon group such as a norbornyl group and a adamantyl group.
- Optional number of hydrogen atoms in these alkyl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group and an ester group.
- a substituted or unsubstituted liner, branched or cyclic alkenyl group for R 1 , R 2 , R 3 and R 4 is not particularly limited, and includes, for example, alkenyl groups having 2 to 20 carbon atoms.
- alkenyl groups there can be mentioned vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenyl, cyclododecenyl, cyclotridecenyl, cyclotetradecen
- the substituted or unsubstituted alkenyl group includes polycyclic hydrocarbon group such as a norbornenyl group.
- Optional number of hydrogen atoms in these alkenyl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group and an ester group.
- a substituted or unsubstituted alkoxy group for R 3 and R 4 is represented by the following formula (8): OR 7 (8) wherein R 7 represents a substituted or unsubstituted linear, branched or cyclic alkyl group.
- the substituted or unsubstituted linear, branched or cyclic alkyl group includes, for example, those which are recited above.
- the substituted or unsubstituted alkoxy group includes, for example, alkoxy groups having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and, as specific examples thereof, there can be mentioned methoxy, ethoxy, isopropoxy, t-butoxy and benzyloxy groups.
- a substituted or unsubstituted aryloxy group for R 3 and R 4 is represented by the following formula (9): OR 8 (9) wherein R 8 represents a substituted or unsubstituted aryl group.
- the substituted or unsubstituted aryl group R 8 includes, for example, substituted or unsubstituted aryl groups having 1 to 4 rings and 6 to 18 carbon atoms, and, as specific examples thereof, those which are recited above as examples of the aryl groups for R 3 and R 4 are mentioned.
- the substituted or unsubstituted aryloxy group of the formula (9) includes, for example, a phenoxy group and a 2,4,6-trimethylphenoxy group.
- a substituted or unsubstituted silyl group for R 3 and R 4 is not particularly limited, and includes, for example, silyl groups having three substituents selected from the group consisting of alkyl groups and aryl groups. More specifically, such silyl group includes, for example, those which have three substituents selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and aryl groups, examples of which are recited above. The three substituents may be the same or different.
- R 3 and R 4 may be bonded together to form a ring with the carbon atoms to which R 3 and R 4 are bonded.
- univalent anion represented by X - there can be mentioned F - , Cl - , Br - , I - , [OSO 2 CH 3 ] - , [OSO 2 CF 3 ] - , [OSO 2 C 6 H 4 CH 3 ] - , [N(SO 2 CF 3 ) 2 ] - , [N(SO 2 C 6 H 4 CH 3 ) 2 ] - , [N(SO 2 CH 3 ) 2 ] - , BF 4 - , BAr 4 - , PF 6 - , AsF 6 - , SbF 6 - , C 6 F 5 and ClO 4 - .
- nitrogen-containing heterocyclic compound represented by the formula (1A) or (1B) there can be mentioned 1,3-bis(2,6-diisopropylphenyl)imidazolinium chloride, 1,3-bis(2,6-diisopropylphenyl)imidazolinium tetrafluoroborate, 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride, 1,3-bis(2,6-diisopropylphenyl)imidazolium tetrafluoroborate, 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazolinium chloride, 1,3-bis(2,4,6-trimethylphenyl)imidazolinium tetra
- nitrogen-containing heterocyclic compounds especially preferable are those in which R 1 and R 2 are an aryl group, preferably a phenyl group, having 1 to 3 substituents, preferably alkyl groups having 1 to 6 carbon atoms, or are an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, and R 3 and R 4 are a hydrogen atom.
- the above-recited nitrogen-containing heterocyclic compounds are publicly known compounds or can easily be prepared by known processes.
- the relative amounts of the nickel metal source, the fluorine source and the nitrogen-containing heterocyclic compound in the first catalyst composition are appropriately chosen in the following ranges: fluorine atom 1 to 10 moles, preferably 1 to 5 moles, per 1 mole of the nickel metal source, and nitrogen-containing heterocyclic compound 1 to 10 moles, preferably 1 to 5 moles, per 1 mole of the nickel metal source.
- the first catalyst composition can be prepared by combining the above-mentioned nickel metal source, fluorine source and nitrogen-containing heterocyclic compound.
- the procedure of combining the three ingredients includes, for example, a procedure of mixing together the above-mentioned three ingredients, and a procedure of adding the three ingredients separately in a solution for a cross-coupling reaction thereby forming the first catalyst composition within the reactive solution.
- the state of the three ingredients is not particularly limited, and they may be present discretely, or at least part of the three ingredients may form a complex.
- the first catalyst composition may further comprise an organic phosphorus compound.
- the organic phosphorus compound includes, for example, phosphines and phosphites, and, as specific examples thereof, there can be mentioned phosphines such as triphenylphosphine, trimethylphosphine, tricyclohexylphosphine, tri-t-butylphosphine, bisdiphenylphosphinoethane, and bisdiphenylphosphinopropane; and phosphites such as trimethoxyphosphite, triethoxyphosphite and triphenoxyphosphite.
- phosphines such as triphenylphosphine, trimethylphosphine, tricyclohexylphosphine, tri-t-butylphosphine, bisdiphenylphosphinoethane, and bisdiphenylphosphinopropane
- phosphites such as trimethoxyphos
- the relative amounts of the nitrogen-containing heterocyclic compound and the organic phosphorus compound are such that the amount of the nitrogen-containing heterocyclic compound is usually in the range of 1 to 5 moles, preferably 2 to 3 moles, per 1 mole of the organic phosphorus compound.
- the first catalyst composition may further comprise, as optional ingredients, an amine compound such as pyridine, triethylamine or N,N,N',N'-tetramethylethylenediamine; a typical metal halide such as zinc chloride, zinc bromide or sodium iodide; and unsaturated hydrocarbons such as ethylene, styrene, butadiene, cyclooctadiene, norbornadiene or diphenylacetylene.
- an amine compound such as pyridine, triethylamine or N,N,N',N'-tetramethylethylenediamine
- a typical metal halide such as zinc chloride, zinc bromide or sodium iodide
- unsaturated hydrocarbons such as ethylene, styrene, butadiene, cyclooctadiene, norbornadiene or diphenylacetylene.
- the amounts of the optional ingredients are appropriately chosen in the range of 1 to 99% by mo
- the second type catalyst composition according to the present invention comprises a nickel metal source, a fluorine source and a phosphine compound.
- the second type catalyst composition containing the phosphine compound is hereinafter referred to as "second catalyst composition" when appropriate.
- the nickel metal source and the fluorine source in the second catalyst composition are the same as mentioned above for the first catalyst composition.
- nickel fluoride is capable of giving a nickel metal and simultaneously a fluorine atom to the catalyst system, therefore, nickel fluoride can be used alone as the nickel metal source and the fluorine source, as explained for the first catalyst composition.
- Nickel fluoride is especially preferable in view of low cost, high reactivity and high stability.
- the phosphine compound in the second catalyst composition is represented by the following formula. wherein R 8 , R 9 and R 10 represent a substituted or unsubstituted aryl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted arylalkyl group, or a substituted or unsubstituted linear, branched or cyclic alkyl group.
- the phosphine compound used in the second catalyst composition is not particularly limited, but, from a viewpoint of availability and economy, preferable examples thereof are trimethylphosphine, tri-t-butylphosphine, tricyclohexylphosphine, triphenylphosphine, tri(p-tolyl)phosphine, bisdiphenylphosphinoethane and bisdiphenylphosphinopropane.
- the relative amounts of the nickel metal source, the fluorine source and the phosphine compound in the second catalyst composition are appropriately chosen in the following ranges: fluorine atom 1 to 10 moles, preferably 1 to 5 moles, per 1 mole of the nickel metal source, and phosphine compound 1 to 10 moles, preferably 1 to 5 moles, per 1 mole of the nickel metal source.
- the second catalyst composition can be prepared by combining the above-mentioned nickel metal source, fluorine source and phosphine compound.
- the procedure of combining the three ingredients includes, for example, a procedure of mixing together the above-mentioned three ingredients, and a procedure of adding the three ingredients separately in a solution for a cross-coupling reaction thereby forming the second catalyst composition within the reactive solution.
- the state of the three ingredients is not particularly limited, and they may be present discretely, or at least part of the three ingredients may form a complex.
- the second catalyst composition may further comprise an organic phosphorus compound.
- the organic phosphorus compound includes, for example, phosphites, and, as specific examples of the phosphites, there can be mentioned trimethoxyphosphite, triethoxyphosphite and triphenoxyphosphite.
- trimethoxyphosphite trimethoxyphosphite
- triethoxyphosphite triethoxyphosphite
- triphenoxyphosphite triphenoxyphosphite.
- the relative amounts of the phosphine compound and the organic phosphorus compound are such that the amount of the phosphine compound is usually in the range of 1 to 5 moles, preferably 2 to 3 moles, per 1 mole of the organic phosphorus compound.
- the second catalyst composition may further comprise, as optional ingredients, an amine compound such as pyridine, triethylamine or N,N,N',N'-tetramethylethylenediamine; a typical metal halide such as zinc chloride, zinc bromide or sodium iodide; and unsaturated hydrocarbons such as ethylene, styrene, butadiene, cyclooctadiene, norbornadiene or diphenylacetylene.
- an amine compound such as pyridine, triethylamine or N,N,N',N'-tetramethylethylenediamine
- a typical metal halide such as zinc chloride, zinc bromide or sodium iodide
- unsaturated hydrocarbons such as ethylene, styrene, butadiene, cyclooctadiene, norbornadiene or diphenylacetylene.
- the amounts of the optional ingredients are appropriately chosen in the range of 1 to 99% by mo
- the above-mentioned two types of the catalyst composition i.e., the first and second catalyst compositions may additionally comprise as other catalyst ingredients at least one metal source selected from the group consisting of an iron metal source and a cobalt metal source.
- the iron metal source is capable of giving an iron metal to a catalyst system.
- the iron metal source is not particularly limited, and, as specific examples thereof, there can be mentioned an iron powder; iron-containing compounds such as iron (II) chloride, iron(III) chloride, iron(II) bromide, iron(III) bromide, iron(II) iodide, iron(II) fluoride, iron(III) fluoride, iron(II) acetate, iron(II) oxalate, iron(III) oxalate, iron(III) citrate, iron(III) perchlorate, iron(III) acetylacetonate, iron(III) nitrate, iron(III) phosphate and iron(II) sulfate; hydrates of these iron-containing compounds; and complex catalysts derived from these iron-containing compounds.
- iron-containing compounds such as iron (II) chloride, iron(III) chloride, iron(II) bromide, iron(III) bromide, iron(II) iodide, iron(I
- the cobalt metal source is capable of giving a cobalt metal to a catalyst system.
- the cobalt metal source is not particularly limited, and, as specific examples thereof, there can be mentioned a cobalt powder; cobalt-containing compounds such as cobalt(II) chloride, cobalt(II) bromide, cobalt(II) iodide, cobalt(II) fluoride, cobalt(II) acetate, cobalt(III) acetate, cobalt(II) formate, cobalt(II) oxalate, cobalt(II) benzoate, cobalt(II) stearate, cobalt(II) borate, cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, cobalt(II) carbonate, cobalt(II) sulfate, cobalt (II) nitrate and cobalt (I
- the relative amounts of the iron metal source and the cobalt metal source in each of the first and second catalyst compositions are such that the amount of each of the iron metal source and the cobalt metal source in each catalyst composition is in the range of 0.1 to 5 moles per 1 mole of the nickel metal source.
- a substituted or unsubstituted aryl group for R 5 and R 6 includes, for example, substituted or unsubstituted aryl groups having 1 to 4 rings and 5 to 18 carbon atoms.
- the aryl groups there can be mentioned phenyl, naphthyl, anthracenyl, azulenyl, pyrenyl, phenanthrenyl and fluorenyl groups.
- Optional number of hydrogen atoms in these aryl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group and an ester group.
- substituents include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner,
- a substituted or unsubstituted heteroaryl group for R 5 and R 6 includes, for example, substituted or unsubstituted heteroaryl groups having 1 to 4 rings and 5 to 18 carbon atoms.
- the heteroaryl groups there can be mentioned pyridyl, pyrimidyl, pyridazyl, pyrazyl, triazyl, benzofuranyl, indolyl, benzothiofenyl, quinolyl, isoquinolyl, carbazolyl, acridinyl, phenanthrolinyl and phenothiazinyl groups.
- Optional number of hydrogen atoms in these heteroaryl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group and an ester group.
- substituents include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner,
- a substituted or unsubstituted linear, branched or cyclic alkyl group for R 5 and R 6 includes, for example, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms.
- the alkyl groups there can be mentioned methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,
- the substituted or unsubstituted alkyl group includes polycyclic hydrocarbon group such as a norbornal group and a adamantyl group.
- Optional number of hydrogen atoms in these alkyl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group and an ester group.
- a substituted or unsubstituted liner, branched or cyclic alkenyl group for R 5 and R 6 includes, for example, alkenyl groups having 2 to 20 carbon atoms.
- alkenyl groups there can be mentioned vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononeny
- the substituted or unsubstituted alkenyl group includes polycyclic hydrocarbon group such as a norbornyl group.
- Optional number of hydrogen atoms in these alkenyl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group and an ester group.
- a halogen atom for Y 1 includes, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- the amount of the catalyst composition used for the cross-coupling according to the present invention is such that the amount of nickel atom in the catalyst composition is in the range of 0.001 to 0.15 equivalent, preferably 0.001 to 0.05 equivalent, based on the compound represented by the formula (4). When the amount is smaller than 0.001 equivalent, the reaction does not proceed smoothly. In contrast, when the amount is larger than 0.15 equivalent, the yield does not increase with an increase of the catalyst amount and the process is disadvantageous from cost consideration.
- the relative amount of the compound represented by the formula (2) or (3) and the compound represented by the formula (4) is such that the compound of formula (4) is in the range of 0.5 to 1 mole, preferably 0.7 to 1 mole, per 1 mole of the compound of formula (2) or (3).
- the procedures adopted in the process for cross-coupling according to the present invention vary depending upon the reaction medium and other conditions, but the cross-coupling reaction is carried usually at a temperature in the range of 0 to 150°C, preferably 60 to 120°C, usually for 6 to 48 hours, preferably 12 to 36 hours, in an argon or nitrogen gas atmosphere.
- the catalyst composition in the process of the present invention may further comprise, as optional ingredients, an amine compound such as pyridine, triethylamine or N,N,N',N'-tetramethylethylenediamine; a typical metal halide such as zinc chloride, zinc bromide or sodium iodide; and unsaturated hydrocarbons such as ethylene, styrene, butadiene, cyclooctadiene, norbornadiene or diphenylacetylene.
- an amine compound such as pyridine, triethylamine or N,N,N',N'-tetramethylethylenediamine
- a typical metal halide such as zinc chloride, zinc bromide or sodium iodide
- unsaturated hydrocarbons such as ethylene, styrene, butadiene, cyclooctadiene, norbornadiene or diphenylacetylene.
- the amounts of the optional ingredients are appropriately chosen in the range of
- the cross-coupling reaction is usually carried out using the conventional reaction medium which does not give a baneful influence on the reaction.
- the reaction medium there can be mentioned ether solvents such as tetrahydrofuran (THF), diethyl ether, tetrahydropyran (THP), 1,4-dioxane, dibutyl ether, methylcyclohexyl ether and 1,2-dimethoxyethane; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone (NMP) and hexamethylphosphoramide (HMPA); halogenated hydrocarbon solvents such as methylene chloride, ethylene chloride and 1,2-dichlorobenzene; aromatic hydrocarbon solvents such as benzene, toluene, xylene and mesitylene; and other organic solvents.
- ether solvents such as tetrahydrofur
- washing such as acid washing, water washing and/or aqueous alkali washing are carried out to remove inorganic by-products and unreacted raw materials from a reaction product.
- Ordinary purification technique such as chromatography, distillation and recrystallization can be adopted to give a target cross-coupled compound.
- Example 1 By the same procedures as described in Example 1, the target compound was synthesized wherein the catalyst composition and the organic halide and the reaction conditions, shown in Table 1, were adopted instead of those as adopted in Example 1. All other conditions remained the same. The results obtained in Examples 1-15 are shown in Table 1.
- acac refers to an acetylacetonato group
- the chemical formulae: SIPr•HCl, IPr•HCl, IPr•HBF4, IPr, I-t-Bu•HCl, PPh 3 , P(t-Bu) 3 and NiCl 2 (dppp) refer to the following compounds, respectively.
- Example 1 NiF 2 (1.0) IPr ⁇ HCl(2.0) Cl 18 96 0 3
- Example 2 NiF 2 ⁇ 4H 2 O(1.0) IPr ⁇ HCl(2.0) Cl 18 96 0 3
- Example 3 NiF 2 ⁇ 4H 2 O(0.5) SIPr ⁇ HCl(1.5) Br 4 98 1 1
- Example 4 NF 2 (0.5) IPr ⁇ HCl(0.5) Br 4 98 2 4
- Example 5 NiCl 2 (0.5), KF(2.0) IPr ⁇ HCl(2.0) Br 1 89 6 12
- Example 6 NiF 2 (0.5), FeF 3 ⁇ 3H 2 O(0.5) IPr ⁇ HCl(2.0) Cl 8 90 1 4
- Example 7 NiF 2 (0.5), CoF 2 ⁇ 4H 2 O(0.5) IPr ⁇ HCl(2.0) Cl 96 94 3 9
- Example 8 NiF 2 (0.33), FeF 3 ⁇ 3H 2 O(0.33), CoF 2 ⁇ 4H 2 O(0.33), CoF 2 ⁇ 4H 2
- NiCl 2 (1.0) IPr ⁇ HCl(2.0) Cl 15 64 18 23 Co.Ex. 2 Ni(acac) 2 (5.0) IPr ⁇ HCl(5.0) Cl 4 46 11 30 Co.Ex. 3 NiF 2 (0.9) -- Br 22 59 32 40 Co.Ex. 4 NiCl 2 (dppp)(0.5) -- Br 8 80 3 25 Co.Ex. 5 NiCl 2 (1.0) PPh 3 (4.0) Br 1 84 8 22
- NiF 2 (2.90 mg, 0.03 mmol, available from Sigma-Aldrich Corp.)
- 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (25.5 mg, 0.06 mmol, available from Sigma-Aldrich Corp.)
- bromobenzene (157.0 mg, 1.0 mmol, available form Wako Pure Chem. Ind., Ltd.) were added, and the obtained mixture was reacted at room temperature for 24 hours. Then, 3.0 ml of a saturated aqueous ammonium chloride solution was added to the reaction mixture, and then 3.0 ml of hexane was added thereto. The reaction mixture was filtered by using a celite pad.
- the celite pad was washed with diethyl ether, and the organic phase was separated from the aqueous phase and then dried over sodium sulfate anhydride. Gas chromatography analysis of the dried organic phase revealed that the yield of target compound was 98%.
- the amounts of homo-coupled compounds derived from bromobenzene and p-tolylmagnesium bromide were 0% and 1%, respectively.
- the catalyst composition according to the present invention is expected to be applied not only for the coupling reaction using a Grignard compound as in the production process of the present invention, but also for other coupling reactions, such as, for example, a coupling reaction using an organoboron compound, a coupling reaction using an organozinc compound, a coupling reaction using an organosilicon compound, a coupling reaction using an organotin compound, a Heck reaction and a Heck-amination reaction.
- Typical examples of the cross-coupled compounds produced by the process using the catalyst composition according to the present invention are unsymmetrical biaryl compounds suitable as liquid crystals and intermediates for medicines.
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Abstract
Description
- This invention relates to a catalyst composition exhibiting a high catalytic activity and selectivity for a cross-coupling reaction in organic syntheses, and a process for producing a coupled compound using the catalyst composition.
Various functional compounds can be produced with an enhanced efficiency by the process according to the present invention. More specifically, unsymmetrical biaryl compounds and other compounds which are useful, for example, as liquid crystal or a raw material for medicines can be produced with an enhanced efficiency. - Unsymmetrical biaryl compounds characterized as having stability due to their aromatic rings and fixed molecular structure are very useful as electronic materials, and intermediates for the synthesis of medicines and pesticides, and various functional compounds.
Unsymmetrical biaryl compounds have heretofore been produced widely by a process comprising cross-coupling an organic halide with an organometallic compound in the presence of a catalyst. Among others, processes utilizing a coupling reaction of an organometallic compound such as an organomagnesium compound or a organozinc compound with an organic halide are well known as an inexpensive cross-coupling reaction process (see, for example,JP H04-173756 A1 JP 2000-95713 A1 - In the above-mentioned processes, a nickel catalyst or a palladium catalyst are usually used as a catalyst. However, these processes have problems. That is, in the case when a nickel catalyst is used, homo-coupled compounds derived from an organometallic compound or an organic halide are produced in large amounts by side reactions. Purification of the thus-synthesized unsymmetrical biaryl compounds required for use as liquid crystal and intermediate for medicines is very costly. In the case when a palladium catalyst is used, the catalyst is expensive and the process is costly and industrially not advantageous.
- Recently, as for the cross-coupling reaction between an organometallic compound with an organic halide, a process using a catalyst comprising a combination of a nickel compound with an N-heterocyclic compound has been proposed (see, for example, Angewandte Chemie International Edition, Germany, 2000, vol. 39, p1602-1604, especially, supporting information Tables 1 to 4). The cross-coupling reaction in this proposed process gives a relatively high yield of the target compound, but the above-mentioned problem of production of undesirable homo-coupled compounds by side reactions still remains unsolved. The experiments conducted by the present inventors revealed that a large amount of the homo-coupled compounds are produced by side reactions. Therefore, the proposed process is still industrially not advantageous.
- An object of the present invention is to provide a catalyst composition exhibiting high activity and selectivity for the cross-coupling reaction for which an industrially satisfying process has not been heretofore proposed, especially a catalyst which does not produce homo-coupled compounds by side reactions from an organometallic compound or an organic halide.
Another object of the present invention is to provide a process for producing a cross-coupled compound using the above-mentioned catalyst composition. - The present inventors made extensive research to solve the foregoing problems of the prior art, and have found that a novel catalyst composition comprising a nickel metal source, a fluorine source and a nitrogen-containing heterocyclic compound having a specific structure, or a phosphine compound exhibits very high activity and selectivity for the cross-coupling reaction of an organometallic compound such as an organomagnesium compound or a organozinc compound with an organic halide, and said catalyst does not cause the problem of producing homo-coupled compounds by side reactions.
- In accordance with the present invention, there is provided a catalyst composition for a cross-coupling reaction comprising a nickel metal source, a fluorine source, and a nitrogen-containing heterocyclic compound represented by the following formula (1A) or (1B), or a phosphine compound:
-
- R1 and R2 may be the same or different and represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkyl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group,
R3 and R4 may be the same or different and represent a hydrogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted silyl group, and R3 and R4 may be bonded together to form a ring with the carbon atoms to which R3 and R4 are bonded, and -
- - - - - -
represents a single bond or a double bond, and
X- represents a univalent anion. - In accordance with the present invention, there is further provided a process for producing a cross-coupled compound represented by the following general formula (5):
R5-R6 (5)
wherein R5 and R6 represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkyl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group, - which comprises allowing an organometallic compound represented by the following general formula (2) or (3):
R5 - MY1 (2)
R5 - M - R5 (3)
wherein R5 is the same as defined above, M represents a magnesium metal or a zinc metal, and Y1 represents a halogen atom, - to react with a compound represented by the following general formula (4):
R6-Y2 (4)
wherein R6 is the same as defined above, and Y2 represents a halogen atom, a methanesulfonate group, a toluenesulfonate group or a trifluoromethanesulfonate group,
in the presence of at least one catalyst composition as mentioned above. - The catalyst composition according to the present invention is a novel catalyst composition, which has not heretofore been proposed, and exhibits high activity and selectivity for a cross-coupling reaction. That is, this catalyst composition suppresses to a great extent the production of undesirable homo-coupled compounds by side reactions, to give the desired cross-coupled compound with a very high selectivity.
By using the catalyst composition according to the present invention, the cross-coupling reaction, for which an industrially satisfying process has not heretofore been proposed, can be industrially advantageously conducted. Especially, unsymmetrical biaryl compounds and other compounds which are useful as liquid crystal or a raw material for medicines can be produced with enhanced yield and selectivity. The catalyst composition according to the present invention does not contain an expensive metal such as palladium, therefore the coupling reaction using the catalyst composition is advantageous from an economical and industrial viewpoint. - The invention will be described in detail.
[Catalyst Composition for Cross-coupling Reaction]
The catalyst composition of the present invention is classified into two types.
A first type of the catalyst composition comprises a nickel metal source, a fluorine source and a nitrogen-containing heterocyclic compound of the following general formula (1A) or (1B): -
- In the above formulae, R1 and R2 may be the same or different and represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkyl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group. R3 and R4 may be the same or different and represent a hydrogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted silyl group. R3 and R4 may be bonded together to form a ring with the carbon atoms to which R3 and R4 are bonded.
-
- - - - - -
represents a single bond or a double bond, and X- represents a univalent anion.
The above-mentioned nitrogen-containing heterocyclic compound represented by the formula (1A) or (1B) is hereinafter referred to as "nitrogen-containing heterocyclic compound" when appropriate, and the first type catalyst composition containing this nitrogen-containing heterocyclic compound according to the present invention is hereinafter referred to as "first catalyst composition" when appropriate. - The nickel metal source, which is one essential ingredient of the first catalyst composition, is capable of giving a nickel metal to a catalyst system. The nickel source is not particularly limited, and is usually selected from nickel salts with a valency of 0 to 2, and complex compounds derived from the nickel salts.
As specific examples of the nickel metal source, there can be mentioned nickel(0) powder; nickel halides such as nickel(II) fluoride, nickel(II) chloride, nickel(II) bromide and nickel(II) iodide; inorganic nickel salts such as nickel(II) sulfate, nickel (II) nitrate, nickel (II) perchlorate and nickel (II) sulfide; and organic acid nickel salts such as nickel(II) formate, nickel(II) oxalate, nickel(II) acetate, nickel(II) fumarate, nickel(II) lactate, nickel(II) gluconate, nickel(II) benzoate, nickel (II) stearate, nickel (II) sulfamate, nickel (II) amidosulfate, nickel(II) carbonate and nickel(II) acetylacetonate. - The complex compounds derived from the nickel salts are not particularly limited, but usually include those which are represented by the following general formula (7):
LcNiXd (7)
wherein L represents a phosphine ligand, an amine ligand or a carbonyl ligand, and, when L is plural, they may be the same or different. These ligands may be crosslinked. c represents an integer in the range of 0 to 6. Ni has a valency of 0 to 2. X represents a halogen atom, a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and, when X is plural, they may be the same or different. d represents a number equal to the number for valency of Ni. - As specific examples of the Ni complex compound, there can be mentioned bis(1,5-cyclooctadiene)nickel(0), bis(allyl)nickel(0), tetracarbonylnickel(0), tricarbonyl(triphenylphosphine)nickel(0), dicarbonylbis(triphenylphosphine)nickel(0), tetrakis(triphenylphosphine)nickel(0), bis[bis(tricyclohexylphosphine)nickel(0) dinitride, (ethylene)bis(triphenylphosphine)nickel(0), (cyclododecatriene)nickel(0), tris(triphenylphosphine)nickel(I) chloride, tris(triphenylphosphine)nickel(I) bromide, tris(triphenylphosphine)nickel(I) iodide, bis(triphenylphosphine)nickel(II) dichloride, bis(triphenylphosphine)nickel(II) dibromide, bis(triphenylphosphine)nickel(II) diiodide, [1,2-bis(diphenylphosphino)ethane]nickel(II) dichloride, [1,2-bis(diphenylphosphino)ethane]nickel(II) dibromide, [1,2-bis(diphenylphosphino)ethane]nickel(II) diiodide, [1,3-bis(diphenylphosphino)propane]nickel(II) dichloride, [1,3-bis(diphenylphosphino)propane]nickel(II) dibromide, [1,3-bis(diphenylphosphino)propane]nickel(II) diiodide, bis(tri-t-butylphosphine)nickel(II) dichloride, bis(tri-t-butylphosphine)nickel(II) dibromide, bis(tri-t-butylphosphine)nickel(II) diiodide, [1,2-bis(di-t-butylphosphino)ethane]nickel(II) dichloride, [1,2-bis(di-t-butylphosphino)ethane]nickel(II) dibromide, [1,2-bis(di-t-butylphosphino)ethane]nickel(II) diiodide, [1,3-bis(di-t-butylphosphino)propane]nickel(II) dichloride, [1,3-bis(di-t-butylphosphino)propane]nickel(II) dibromide, [1,3-bis(di-t-butylphosphino)propane]nickel(II) diiodide, [1,2-bis(dicyclohexylphosphino)ethane]nickel(II) dichloride, [1,2-bis(dicyclohexylphosphino)ethane]nickel(II) dibromide, [1,2-bis(dicyclohexylphosphino)ethane]nickel(II) diiodide, [1,3-bis(dicyclohexylphosphino)propane]nickel(II) dichloride, [1,3-bis(dicyclohexylphosphino)propane]nickel(II) dibromide, [1,3-bis(dicyclohexylphosphino)propane]nickel(II) diiodide, bis(tricyclohexylphosphine)nickel(II) dichloride, bis(tricyclohexylphosphine)nickel(II) dibromide, bis(tricyclohexylphosphine)nickel(II) diiodide, bis(trimethylphosphine)nickel(II) dichloride, bis(trimethylphosphine)nickel(II) dibromide, bis(trimethylphosphine)nickel(II) diiodide, bis(triethylphosphine)nickel(II) dichloride, bis(triethylphosphine)nickel(II) dibromide, bis(triethylphosphine)nickel(II) diiodide, bis(tri-i-propylphosphine)nickel(II) dichloride, bis(tri-i-propylphosphine)nickel(II) dibromide, bis(tri-i-propylphosphine)nickel(II) diiodide, bis(tri-n-butylphosphine)nickel(II) dichloride, bis(tri-n-butylphosphine)nickel(II) dibromide, bis(tri-n-butylphosphine)nickel(II) diiodide, bis(methyldiphenylphosphine)nickel(II) dichloride, bis(methyldiphenylphosphine)nickel(II) dibromide, bis(methyldiphenylphosphine)nickel(II) diiodide, bis(dimethylphenylphosphine)nickel(II) dichloride, bis(dimethylphenylphosphine)nickel(II) dibromide, bis(dimethylphenylphosphine)nickel(II) diiodide, (phenyl)bis(triphenylphosphine)nickel(II) chloride, (phenyl)bis(triphenylphosphine)nickel(II) bromide, (phenyl)bis(triphenylphosphine)nickel(II) iodide, dimethylbis(trimethylphosphine)nickel(II), tetramethylenebis(triphenylphosphine)nickel(II), (cyclopentadienyl)(triphenylphosphine)nickel(II) chloride, methyl(cyclopentadienyl)(triphenylphosphine)nickel(II), bis(tricyclohexylphosphine)nickel(II) chloride hydride, (2,2'-bipyridyl)nickel(II) dichloride, (2,2'-bipyridyl)nickel(II) dibromide, (2,2'-bipyridyl)nickel(II) diiodide, diethyl(2,2'-bipyridyl)nickel(II), bis(triethylamine)nickel dichloride, bis(triethylamine)nickel dibromide, bis(triethylamine)nickel diiodide, bis(pyridine)nickel dichloride, bis(pyridine)nickel dibromide, bis(pyridine)nickel diiodide, (N,N,N',N'-tetramethylethylenediamine)nickel dichloride, (N,N,N',N'-tetramethylethylenediamine)nickel dibromide, and (N,N,N',N'-tetramethylethylenediamine)nickel diiodide.
The above-listed complex compounds may be used either alone or as a mixture thereof. - The fluorine source, which is one essential ingredient of the first catalyst composition, is capable of giving a fluorine atom to a catalyst system.
The fluorine source is not particularly limited, and, as specific examples thereof, there can be mentioned fluorine gas, hydrofluoric acid, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, beryllium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, scandium fluoride, yttrium fluoride, lanthanum fluoride, titanium fluoride, zirconium fluoride, hafnium fluoride, vanadium fluoride, niobium fluoride, tantalum fluoride, chromium fluoride, molybdenum fluoride, tungsten fluoride, manganese fluoride, ruthenium fluoride, osmium fluoride, rhodium fluoride, iridium fluoride, nickel fluoride, palladium fluoride, copper fluoride, silver fluoride, zinc fluoride, cadmium fluoride, boron fluoride, aluminum fluoride, gallium fluoride, indium fluoride, thallium fluoride, tin fluoride, lead fluoride, antimony fluoride, ammonium fluoride, potassium titanium fluoride, samarium fluoride, hydrogen fluoride-pyridine, hydrosilicofluoric acid, sodium silicofluoride, potassium silicofluoride, ammonium silicofluoride, magnesium silicofluoride, hydroborofluoric acid, sodim borofluoride, potassium borofluoride, iron borofluoride, zinc borofluoride, copper borofluoride, tin borofluoride, ammonium borofluoride and lithium hexafluorophosphate.
The above-listed compounds may be used either alone or as a mixture thereof. - Nickel fluoride is capable of giving a nickel metal and simultaneously a fluorine atom to the catalyst system, therefore, nickel fluoride can be used alone as the nickel metal source and the fluorine source. Nickel fluoride is especially preferable in view of low cost, high reactivity and high stability.
The first catalyst composition comprises, in addition to the above-mentioned nickel metal source and fluorine source, a nitrogen-containing heterocyclic compound of the following general formula (1A) or (1B) as an essential ingredient. -
- In the above formulae (1A) and (1B), a substituted or unsubstituted aryl group for R1, R2, R3 and R4 is not particularly limited, and includes, for example, substituted or unsubstituted aryl groups having 1 to 4 rings and 6 to 18 carbon atoms. As specific examples of the aryl groups, there can be mentioned phenyl, naphthyl, anthracenyl, azulenyl, pyrenyl, phenanthrenyl and fluorenyl groups.
Optional number of hydrogen atoms in these aryl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group, an ester group and an silyl group. - A substituted or unsubstituted heteroaryl group for R1, R2, R3 and R4 is not particularly limited, and includes, for example, substituted or unsubstituted heteroaryl groups having 1 to 4 rings and 6 to 18 carbon atoms. As specific examples of the heteroaryl groups, there can be mentioned pyridyl, pyrimidyl, pyridazyl, pyrazyl, triazyl, benzofuranyl, indolyl, benzothiofenyl, quinolyl, isoquinolyl, carbazolyl, acridinyl, phenanthrolinyl and phenothiazinyl groups.
Optional number of hydrogen atoms in these heteroaryl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group and an ester group. - A substituted or unsubstituted linear, branched or cyclic alkyl group for R1, R2, R3 and R4 is not particularly limited, and includes, for example, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. As specific examples of the alkyl groups, there can be mentioned methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, cyclopentadecyl, cyclohexadecyl, cycloheptadecyl, cyclooctadecyl, cyclononadecyl and cycloeicosyl groups. Further, the substituted or unsubstituted alkyl group includes polycyclic hydrocarbon group such as a norbornyl group and a adamantyl group.
Optional number of hydrogen atoms in these alkyl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group and an ester group. - A substituted or unsubstituted liner, branched or cyclic alkenyl group for R1, R2, R3 and R4 is not particularly limited, and includes, for example, alkenyl groups having 2 to 20 carbon atoms. As specific examples of the alkenyl groups, there can be mentioned vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenyl, cyclododecenyl, cyclotridecenyl, cyclotetradecenyl, cyclopentadecenyl, cyclohexadecenyl, cycloheptadecenyl, cyclooctadecenyl, cyclononadecenyl and cycloeicosenyl groups. Further, the substituted or unsubstituted alkenyl group includes polycyclic hydrocarbon group such as a norbornenyl group.
Optional number of hydrogen atoms in these alkenyl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group and an ester group. - A substituted or unsubstituted alkoxy group for R3 and R4 is represented by the following formula (8):
OR7 (8)
wherein R7 represents a substituted or unsubstituted linear, branched or cyclic alkyl group. The substituted or unsubstituted linear, branched or cyclic alkyl group includes, for example, those which are recited above.
The substituted or unsubstituted alkoxy group includes, for example, alkoxy groups having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and, as specific examples thereof, there can be mentioned methoxy, ethoxy, isopropoxy, t-butoxy and benzyloxy groups. - A substituted or unsubstituted aryloxy group for R3 and R4 is represented by the following formula (9):
OR8 (9)
wherein R8 represents a substituted or unsubstituted aryl group. The substituted or unsubstituted aryl group R8 includes, for example, substituted or unsubstituted aryl groups having 1 to 4 rings and 6 to 18 carbon atoms, and, as specific examples thereof, those which are recited above as examples of the aryl groups for R3 and R4 are mentioned.
The substituted or unsubstituted aryloxy group of the formula (9) includes, for example, a phenoxy group and a 2,4,6-trimethylphenoxy group. - A substituted or unsubstituted silyl group for R3 and R4 is not particularly limited, and includes, for example, silyl groups having three substituents selected from the group consisting of alkyl groups and aryl groups. More specifically, such silyl group includes, for example, those which have three substituents selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and aryl groups, examples of which are recited above. The three substituents may be the same or different. As specific examples of the substituted or unsubstituted silyl group, there can be mentioned trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, triphenylsilyl and triisopropylsilyl groups.
R3 and R4 may be bonded together to form a ring with the carbon atoms to which R3 and R4 are bonded. - As specific examples of the univalent anion represented by X-, there can be mentioned F-, Cl-, Br-, I-, [OSO2CH3]-, [OSO2CF3]-, [OSO2C6H4CH3]-, [N(SO2CF3)2]-, [N(SO2C6H4CH3)2]-, [N(SO2CH3)2]-, BF4 -, BAr4 -, PF6 -, AsF6 -, SbF6 -, C6F5 and ClO4 -.
- As specific examples of the nitrogen-containing heterocyclic compound represented by the formula (1A) or (1B), there can be mentioned 1,3-bis(2,6-diisopropylphenyl)imidazolinium chloride, 1,3-bis(2,6-diisopropylphenyl)imidazolinium tetrafluoroborate, 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride, 1,3-bis(2,6-diisopropylphenyl)imidazolium tetrafluoroborate, 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazolinium chloride, 1,3-bis(2,4,6-trimethylphenyl)imidazolinium tetrafluoroborate, 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride, 1,3-bis(2,4,6-trimethylphenyl)imidazolium tetrafluoroborate, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-di-t-butylimidazolinium chloride, 1,3-di-t-butylimidazolinium tetrafluoroborate, 1,3-di-t-butylimidazolidin-2-ylidene, 1,3-di-t-butylimidazolium chloride, 1,3-di-t-butylimidazolium tetrafluoroborate, 1,3-di-t-butylimidazol-2-ylidene, 1,3-bis(1-adamantyl)imidazolinium tetrafluoroborate, 1,3-bis(1-adamantyl)imidazolium tetrafluoroborate and 1,3-bis(1-adamantyl)benzimidazolinium tetrafluoroborate.
- Of the above-recited nitrogen-containing heterocyclic compounds, especially preferable are those in which R1 and R2 are an aryl group, preferably a phenyl group, having 1 to 3 substituents, preferably alkyl groups having 1 to 6 carbon atoms, or are an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, and R3 and R4 are a hydrogen atom.
The above-recited nitrogen-containing heterocyclic compounds are publicly known compounds or can easily be prepared by known processes.
The relative amounts of the nickel metal source, the fluorine source and the nitrogen-containing heterocyclic compound in the first catalyst composition are appropriately chosen in the following ranges: fluorine atom 1 to 10 moles, preferably 1 to 5 moles, per 1 mole of the nickel metal source, and nitrogen-containing heterocyclic compound 1 to 10 moles, preferably 1 to 5 moles, per 1 mole of the nickel metal source. - The first catalyst composition can be prepared by combining the above-mentioned nickel metal source, fluorine source and nitrogen-containing heterocyclic compound. The procedure of combining the three ingredients includes, for example, a procedure of mixing together the above-mentioned three ingredients, and a procedure of adding the three ingredients separately in a solution for a cross-coupling reaction thereby forming the first catalyst composition within the reactive solution. The state of the three ingredients is not particularly limited, and they may be present discretely, or at least part of the three ingredients may form a complex.
- The first catalyst composition may further comprise an organic phosphorus compound. The organic phosphorus compound includes, for example, phosphines and phosphites, and, as specific examples thereof, there can be mentioned phosphines such as triphenylphosphine, trimethylphosphine, tricyclohexylphosphine, tri-t-butylphosphine, bisdiphenylphosphinoethane, and bisdiphenylphosphinopropane; and phosphites such as trimethoxyphosphite, triethoxyphosphite and triphenoxyphosphite.
The relative amounts of the nitrogen-containing heterocyclic compound and the organic phosphorus compound are such that the amount of the nitrogen-containing heterocyclic compound is usually in the range of 1 to 5 moles, preferably 2 to 3 moles, per 1 mole of the organic phosphorus compound. - The first catalyst composition may further comprise, as optional ingredients, an amine compound such as pyridine, triethylamine or N,N,N',N'-tetramethylethylenediamine; a typical metal halide such as zinc chloride, zinc bromide or sodium iodide; and unsaturated hydrocarbons such as ethylene, styrene, butadiene, cyclooctadiene, norbornadiene or diphenylacetylene. In the case when the first catalyst composition comprises the above-mentioned optional ingredients, the amounts of the optional ingredients are appropriately chosen in the range of 1 to 99% by mole based on the total catalyst composition.
- The second type catalyst composition according to the present invention comprises a nickel metal source, a fluorine source and a phosphine compound. The second type catalyst composition containing the phosphine compound is hereinafter referred to as "second catalyst composition" when appropriate.
The nickel metal source and the fluorine source in the second catalyst composition are the same as mentioned above for the first catalyst composition.
In the second catalyst composition, nickel fluoride is capable of giving a nickel metal and simultaneously a fluorine atom to the catalyst system, therefore, nickel fluoride can be used alone as the nickel metal source and the fluorine source, as explained for the first catalyst composition. Nickel fluoride is especially preferable in view of low cost, high reactivity and high stability. - The phosphine compound in the second catalyst composition is represented by the following formula.
- The phosphine compound used in the second catalyst composition is not particularly limited, but, from a viewpoint of availability and economy, preferable examples thereof are trimethylphosphine, tri-t-butylphosphine, tricyclohexylphosphine, triphenylphosphine, tri(p-tolyl)phosphine, bisdiphenylphosphinoethane and bisdiphenylphosphinopropane.
The relative amounts of the nickel metal source, the fluorine source and the phosphine compound in the second catalyst composition are appropriately chosen in the following ranges: fluorine atom 1 to 10 moles, preferably 1 to 5 moles, per 1 mole of the nickel metal source, and phosphine compound 1 to 10 moles, preferably 1 to 5 moles, per 1 mole of the nickel metal source. - The second catalyst composition can be prepared by combining the above-mentioned nickel metal source, fluorine source and phosphine compound. The procedure of combining the three ingredients includes, for example, a procedure of mixing together the above-mentioned three ingredients, and a procedure of adding the three ingredients separately in a solution for a cross-coupling reaction thereby forming the second catalyst composition within the reactive solution. The state of the three ingredients is not particularly limited, and they may be present discretely, or at least part of the three ingredients may form a complex.
- The second catalyst composition may further comprise an organic phosphorus compound. The organic phosphorus compound includes, for example, phosphites, and, as specific examples of the phosphites, there can be mentioned trimethoxyphosphite, triethoxyphosphite and triphenoxyphosphite.
The relative amounts of the phosphine compound and the organic phosphorus compound are such that the amount of the phosphine compound is usually in the range of 1 to 5 moles, preferably 2 to 3 moles, per 1 mole of the organic phosphorus compound. - The second catalyst composition may further comprise, as optional ingredients, an amine compound such as pyridine, triethylamine or N,N,N',N'-tetramethylethylenediamine; a typical metal halide such as zinc chloride, zinc bromide or sodium iodide; and unsaturated hydrocarbons such as ethylene, styrene, butadiene, cyclooctadiene, norbornadiene or diphenylacetylene.
In the case when the second catalyst composition comprises the above-mentioned optional ingredients, the amounts of the optional ingredients are appropriately chosen in the range of 1 to 99% by mole based on the total catalyst composition. - The above-mentioned two types of the catalyst composition, i.e., the first and second catalyst compositions may additionally comprise as other catalyst ingredients at least one metal source selected from the group consisting of an iron metal source and a cobalt metal source.
The iron metal source is capable of giving an iron metal to a catalyst system. The iron metal source is not particularly limited, and, as specific examples thereof, there can be mentioned an iron powder; iron-containing compounds such as iron (II) chloride, iron(III) chloride, iron(II) bromide, iron(III) bromide, iron(II) iodide, iron(II) fluoride, iron(III) fluoride, iron(II) acetate, iron(II) oxalate, iron(III) oxalate, iron(III) citrate, iron(III) perchlorate, iron(III) acetylacetonate, iron(III) nitrate, iron(III) phosphate and iron(II) sulfate; hydrates of these iron-containing compounds; and complex catalysts derived from these iron-containing compounds. - The cobalt metal source is capable of giving a cobalt metal to a catalyst system. The cobalt metal source is not particularly limited, and, as specific examples thereof, there can be mentioned a cobalt powder; cobalt-containing compounds such as cobalt(II) chloride, cobalt(II) bromide, cobalt(II) iodide, cobalt(II) fluoride, cobalt(II) acetate, cobalt(III) acetate, cobalt(II) formate, cobalt(II) oxalate, cobalt(II) benzoate, cobalt(II) stearate, cobalt(II) borate, cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, cobalt(II) carbonate, cobalt(II) sulfate, cobalt (II) nitrate and cobalt (II) phosphate; hydrates of these cobalt-containing compounds; and complex catalysts derived from these cobalt-containing compounds.
The relative amounts of the iron metal source and the cobalt metal source in each of the first and second catalyst compositions are such that the amount of each of the iron metal source and the cobalt metal source in each catalyst composition is in the range of 0.1 to 5 moles per 1 mole of the nickel metal source. - In accordance with the present invention, there is further provided a process for producing a cross-coupled compound represented by the following general formula (5):
R5-R6 (5)
wherein R5 and R6 represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkyl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group,
which comprises allowing an organometallic compound represented by the following general formula (2) or (3):
R5 - MY1 (2)
R5 - M - R5 (3)
wherein R5 is the same as defined above, M represents a magnesium metal or a zinc metal, and Y1 represents a halogen atom,
to react with a compound represented by the following general formula (4):
R6 - Y2 (4)
wherein R6 is the same as defined above, and Y2 represents a halogen atom, a methanesulfonate group, a toluenesulfonate group or a trifluoromethanesulfonate group,
in the presence of a catalyst composition selected from the above-mentioned first catalyst composition and the second catalyst composition. - In the above formulae (2) to (5), a substituted or unsubstituted aryl group for R5 and R6 includes, for example, substituted or unsubstituted aryl groups having 1 to 4 rings and 5 to 18 carbon atoms. As specific examples of the aryl groups, there can be mentioned phenyl, naphthyl, anthracenyl, azulenyl, pyrenyl, phenanthrenyl and fluorenyl groups. Optional number of hydrogen atoms in these aryl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group and an ester group.
- A substituted or unsubstituted heteroaryl group for R5 and R6 includes, for example, substituted or unsubstituted heteroaryl groups having 1 to 4 rings and 5 to 18 carbon atoms. As specific examples of the heteroaryl groups, there can be mentioned pyridyl, pyrimidyl, pyridazyl, pyrazyl, triazyl, benzofuranyl, indolyl, benzothiofenyl, quinolyl, isoquinolyl, carbazolyl, acridinyl, phenanthrolinyl and phenothiazinyl groups.
Optional number of hydrogen atoms in these heteroaryl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group and an ester group. - A substituted or unsubstituted linear, branched or cyclic alkyl group for R5 and R6 includes, for example, linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. As specific examples of the alkyl groups, there can be mentioned methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, cyclopentadecyl, cyclohexadecyl, cycloheptadecyl, cyclooctadecyl, cyclononadecyl and cycloeicosyl groups. Further, the substituted or unsubstituted alkyl group includes polycyclic hydrocarbon group such as a norbornal group and a adamantyl group.
Optional number of hydrogen atoms in these alkyl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group and an ester group. - A substituted or unsubstituted liner, branched or cyclic alkenyl group for R5 and R6 includes, for example, alkenyl groups having 2 to 20 carbon atoms. As specific examples of the alkenyl groups, there can be mentioned vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenyl, cyclododecenyl, cyclotridecenyl, cyclotetradecenyl, cyclopentadecenyl, cyclohexadecenyl, cycloheptadecenyl, cyclooctadecenyl, cyclononadecenyl and cycloeicosenyl groups. Further, the substituted or unsubstituted alkenyl group includes polycyclic hydrocarbon group such as a norbornyl group.
Optional number of hydrogen atoms in these alkenyl groups may be substituted by substituents which include, for example, a halogen atom, a substituted or unsubstituted liner, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted liner, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group and an ester group. - A halogen atom for Y1 includes, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The amount of the catalyst composition used for the cross-coupling according to the present invention is such that the amount of nickel atom in the catalyst composition is in the range of 0.001 to 0.15 equivalent, preferably 0.001 to 0.05 equivalent, based on the compound represented by the formula (4). When the amount is smaller than 0.001 equivalent, the reaction does not proceed smoothly. In contrast, when the amount is larger than 0.15 equivalent, the yield does not increase with an increase of the catalyst amount and the process is disadvantageous from cost consideration. - In the process for producing the cross-coupled compound according to the present invention, the relative amount of the compound represented by the formula (2) or (3) and the compound represented by the formula (4) is such that the compound of formula (4) is in the range of 0.5 to 1 mole, preferably 0.7 to 1 mole, per 1 mole of the compound of formula (2) or (3).
The procedures adopted in the process for cross-coupling according to the present invention vary depending upon the reaction medium and other conditions, but the cross-coupling reaction is carried usually at a temperature in the range of 0 to 150°C, preferably 60 to 120°C, usually for 6 to 48 hours, preferably 12 to 36 hours, in an argon or nitrogen gas atmosphere. - The catalyst composition in the process of the present invention may further comprise, as optional ingredients, an amine compound such as pyridine, triethylamine or N,N,N',N'-tetramethylethylenediamine; a typical metal halide such as zinc chloride, zinc bromide or sodium iodide; and unsaturated hydrocarbons such as ethylene, styrene, butadiene, cyclooctadiene, norbornadiene or diphenylacetylene.
In the case when the catalyst composition used comprises the above-mentioned optional ingredients, the amounts of the optional ingredients are appropriately chosen in the range of 1 to 10 moles per 1 mole of the compound of the formula (4). - The cross-coupling reaction is usually carried out using the conventional reaction medium which does not give a baneful influence on the reaction. As specific examples of the reaction medium, there can be mentioned ether solvents such as tetrahydrofuran (THF), diethyl ether, tetrahydropyran (THP), 1,4-dioxane, dibutyl ether, methylcyclohexyl ether and 1,2-dimethoxyethane; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone (NMP) and hexamethylphosphoramide (HMPA); halogenated hydrocarbon solvents such as methylene chloride, ethylene chloride and 1,2-dichlorobenzene; aromatic hydrocarbon solvents such as benzene, toluene, xylene and mesitylene; and other organic solvents.
After completion of the cross-coupling reaction, washing such as acid washing, water washing and/or aqueous alkali washing are carried out to remove inorganic by-products and unreacted raw materials from a reaction product. Ordinary purification technique such as chromatography, distillation and recrystallization can be adopted to give a target cross-coupled compound. - The present invention will now be specifically described by the following examples that by no means limits the scope of the invention.
-
- GC analysis equipment: GC-17A available from Shimadzu Corporation
- GC column: HR-1 (length 25 m, inner diameter 0.25 mm, membrane thickness 0.25 µm, available from Shinwa Chem. Ind., Ltd. :
- Column temperature: maintained at 40°C for 3 minutes and then elevated to 200°C at a rate of 10°C/min.
- Injection area temperature: 300°C
- Detection area temperature: 300°C (FID)
- Chlorobenzene (327.5 mg, 2.9 mmol, available form Wako Pure Chem. Ind., Ltd.) and a solution (3.18 mL) in tetrahydrofuran (THF) of p-tolylmagnesium bromide (1.13 M, 3. 6 mmol, available from Tokyo Chem. Ind., Ltd.) were added to a mixture of NiF2 (2.90 mg, 0.03 mmol, available from Sigma-Aldrich Corp.) and 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (25.8 mg, 0.06 mmol, available from Sigma-Aldrich Corp.) at 0°C in an argon gas atmosphere, and the obtained mixture was reacted at 60°C for 36 hours. Then, the reaction mixture was cooled to room temperature, and 2.0 ml of a saturated aqueous ammonium chloride solution was added to the reaction mixture. Further, 3.0 ml of hexane was added thereto and an organic phase was separated. Extraction of an aqueous phase with diethyl ether was conducted five times. Gas chromatography analysis of the collected organic extracts revealed that the yield of target compound was 96%. The amounts of homo-coupled compounds derived from chlorobenzene and p-tolylmagnesium bromide were 0% and 3%, respectively.
- By the same procedures as described in Example 1, the target compound was synthesized wherein the catalyst composition and the organic halide and the reaction conditions, shown in Table 1, were adopted instead of those as adopted in Example 1. All other conditions remained the same. The results obtained in Examples 1-15 are shown in Table 1.
- In Table 1, abbreviation "acac" refers to an acetylacetonato group, and the chemical formulae: SIPr•HCl, IPr•HCl, IPr•HBF4, IPr, I-t-Bu•HCl, PPh3, P(t-Bu)3 and NiCl2(dppp) refer to the following compounds, respectively.
-
- By the same procedures as described in Example 1, the target compound was synthesized wherein the catalyst composition and the organic halide and the reaction conditions, shown in Table 1, were adopted instead of those as adopted in Example 1. All other conditions remained the same. The results obtained in Comparative Examples 1-5 are also shown in Table 1.
-
Table 1 metal salt (mol%) addive (mol%) X time (h) yield(%) 1 2 3 Example 1 NiF2(1.0) IPr·HCl(2.0) Cl 18 96 0 3 Example 2 NiF2·4H2O(1.0) IPr·HCl(2.0) Cl 18 96 0 3 Example 3 NiF2·4H2O(0.5) SIPr·HCl(1.5) Br 4 98 1 1 Example 4 NF2(0.5) IPr·HCl(0.5) Br 4 98 2 4 Example 5 NiCl2(0.5), KF(2.0) IPr·HCl(2.0) Br 1 89 6 12 Example 6 NiF2(0.5), FeF3·3H2O(0.5) IPr·HCl(2.0) Cl 8 90 1 4 Example 7 NiF2(0.5), CoF2·4H2O(0.5) IPr·HCl(2.0) Cl 96 94 3 9 Example 8 NiF2(0.33), FeF3·3H2O(0.33), CoF2·4H2O(0.33) IPr·HCl(2.0) Cl 96 84 1 5 Example 9 NiF2(0.5) IPr-HBF4(1.0) Cl 48 98 0 1 Example 10 NiF2(0.5) I-t-BuHCl(1.0) Cl 48 96 0 3 Example 11 iF2(0.5) SIPr·HCl(1.0) Cl 48 94 2 10 Example 12 NiF2(0.5) P(tBu)3(1.0) Cl 16 98 1 1 Example 13 NiF2(0.5) IPr(1.0) Br 1 99 0 1 Example 14 NiF2(1.0) PPh3(4.0) Br 16 98 6 14 Example 15 NiF2(1.0) IPr-HCl(1.0) I 1 92 1 11 Co.Ex. 1 NiCl2(1.0) IPr·HCl(2.0) Cl 15 64 18 23 Co.Ex. 2 Ni(acac)2(5.0) IPr·HCl(5.0) Cl 4 46 11 30 Co.Ex. 3 NiF2(0.9) -- Br 22 59 32 40 Co.Ex. 4 NiCl2(dppp)(0.5) -- Br 8 80 3 25 Co.Ex. 5 NiCl2(1.0) PPh3(4.0) Br 1 84 8 22 - 1-Bromo-3,5-difluorobenzene (589.0mg, 3.05mmol, available form Tokyo Chem. Ind., Ltd.) and a THF solution (4.10 mL) of p-methoxyphenylmagnesium bromide (0.88 M, 3.6 mmol, available from Tokyo Chem. Ind., Ltd.) were added to a mixture of NiF2 (1.45 mg, 0.015 mmol, available from Sigma-Aldrich Corp.) and 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (12.8 mg, 0.03 mmol, available from Sigma-Aldrich Corp.) at 0°C in an argon gas atmosphere, and the obtained mixture was reacted at 60°C for 3 hours. Then, the reaction mixture was cooled to room temperature, and 2.0 ml of a saturated aqueous ammonium chloride solution was added to the reaction mixture. Further, 3.0 ml of hexane was added thereto, and an organic phase was separated. Extraction of an aqueous phase with diethyl ether was conducted five times. Gas chromatography analysis of the collected organic extracts revealed that the yield of target compound was 80%. The amounts of homo-coupled compounds derived from 1-bromo-3,5-difluorobenzene and p-methoxyphenylmagnesium bromide were 0% and 4%, respectively.
- By the same procedures as in Example 16, cross-coupled compounds (Ar1-Ar2) were synthesized wherein the same catalyst composition as used in Example 16 was used, and the organic halide (Ar1-X) and the organomagnesium compound (Ar2MgBr) and the reaction conditions, which are shown in Table 2, were adopted instead of those as adopted in Example 16. All other conditions remained the same. The results obtained in Examples 16-26 are shown in Table 2.
Ar1-X + Ar2MgBr → Ar1-Ar2
-
Table 2 Ar1-X Ar2MgBr
(equiv)NiF2 (X mol%)
IPr·HCl (2X mol%)conditions yield (%) Example 16 X = 0.5 60 °C, 3 h 80 Example 17 X = 3 60 °C, 24 h 88 Example 18 X = 1 60 °C, 36 h 94 Example 19 X = 1 80 °C, 12 h 98 Example 20 X = 1 120 °C, 4 h
(in toluene)96 Example 21 X = 3 60 °C, 24 h 82 Example 22 X = 1 60 °C, 18 h 94 Example 23 X = 0.5 60 or, 16 h 93 Example 24 X = 0.5 60 °C, 16 h 84 Example 25 X = 0.5 60 °C, 18 h 83 Example 26 X = 3 80 °C, 24 h 99 - A THF solution (3.13 mL) of p-tolylmagnesium bromide (0.96 M, 3.0 mmol, available from Tokyo Chem. Ind., Ltd.) was added to a zinc chloride·N,N,N',N'-tetramethylethylenediamine complex (378.8 mg, 1.5 mmol, available from Sigma-Aldrich Corp.) at 0°C in an argon gas atmosphere. To the obtained mixture, NiF2 (2.90 mg, 0.03 mmol, available from Sigma-Aldrich Corp.), 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (25.5 mg, 0.06 mmol, available from Sigma-Aldrich Corp.) and bromobenzene (157.0 mg, 1.0 mmol, available form Wako Pure Chem. Ind., Ltd.) were added, and the obtained mixture was reacted at room temperature for 24 hours. Then, 3.0 ml of a saturated aqueous ammonium chloride solution was added to the reaction mixture, and then 3.0 ml of hexane was added thereto. The reaction mixture was filtered by using a celite pad. The celite pad was washed with diethyl ether, and the organic phase was separated from the aqueous phase and then dried over sodium sulfate anhydride. Gas chromatography analysis of the dried organic phase revealed that the yield of target compound was 98%. The amounts of homo-coupled compounds derived from bromobenzene and p-tolylmagnesium bromide were 0% and 1%, respectively.
- By the same procedures as in Example 27, cross-coupled compounds (Ar1-Ar2) were synthesized wherein the same catalyst composition as used in Example 27 was used, and the organic halide (Ar1-X) and the organozinc compound (Ar2)2Zn and the reaction conditions, which are shown in Table 3, were adopted instead of those as adopted in Example 27. All other conditions remained the same. The results obtained in Examples 27-30 are shown in Table 3.
Ar1 - X + (Ar2)2Zn → Ar1 - Ar2
-
- The catalyst composition according to the present invention is expected to be applied not only for the coupling reaction using a Grignard compound as in the production process of the present invention, but also for other coupling reactions, such as, for example, a coupling reaction using an organoboron compound, a coupling reaction using an organozinc compound, a coupling reaction using an organosilicon compound, a coupling reaction using an organotin compound, a Heck reaction and a Heck-amination reaction.
Typical examples of the cross-coupled compounds produced by the process using the catalyst composition according to the present invention are unsymmetrical biaryl compounds suitable as liquid crystals and intermediates for medicines.
Claims (7)
- A catalyst composition for a cross-coupling reaction comprising a nickel metal source, a fluorine source, and a nitrogen-containing heterocyclic compound represented by the following formula (1A) or (1B), or a phosphine compound:
R1 and R2 may be the same or different and represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkyl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group,
R3 and R4 may be the same or different and represent a hydrogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted linear, branched or cyclic alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted silyl group, and R3 and R4 may be bonded together to form a ring with the carbon atoms to which R3 and R4 are bonded, and
------
represents a single bond or a double bond, and
X- represents a univalent anion. - The catalyst composition for a cross-coupling reaction according to claim 1, wherein the phosphine compound is tri-t-butylphosphine or triphenylphosphine.
- The catalyst composition for a cross-coupling reaction according to claim 1 or 2, wherein the nickel metal source and the fluorine source are nickel fluoride.
- The catalyst composition for a cross-coupling reaction according to any one of claims 1 to 3, which further comprises at least one compound selected from the group consisting of an organic phosphorus compound, an amine compound, a typical metal halide and an unsaturated hydrocarbon.
- The catalyst composition for a cross-coupling reaction according to any one of claims 1 to 4, which further comprises at least one metal source selected from the group consisting of an iron metal source and a cobalt metal source.
- A process for producing a cross-coupled compound represented by the following general formula (5):
R5-R6 (5)
wherein R5 and R6 represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkyl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group,
which comprises allowing an organometallic compound represented by the following general formula (2) or (3):
R5 - MY1 (2)
R5 - M - R5 (3)
wherein R5 is the same as defined above, M represents a magnesium metal or a zinc metal, and Y1 represents a halogen atom,
to react with a compound represented by the following general formula (4):
R6 - Y2 (4)
wherein R6 is the same as defined above, and Y2 represents
a halogen atom, a methanesulfonate group, a toluenesulfonate group or a trifluoromethanesulfonate group,
in the presence of the catalyst composition as claimed in any one of claims 1 to 5. - A process for producing a cross-coupled compound represented by the following general formula (5):
R5-R6 (5)
wherein R5 and R6 represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkyl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group,
which comprises allowing an organomagnesium compound represented by the following general formula (6):
R5 - MgY1 (6)
wherein R5 is the same as defined above, and Y1 represents a halogen atom,
to react with a compound represented by the following general formula (4):
R6 - Y2 (4)
wherein R6 is the same as defined above, and Y2 represents a halogen atom, a methanesulfonate group, a toluenesulfonate group or a trifluoromethanesulfonate group,
in the presence of the catalyst composition as claimed in any one of claims 1 to 5.
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PCT/JP2008/062401 WO2009008447A1 (en) | 2007-07-11 | 2008-07-09 | Catalyst composition and method for producing cross-coupling compound using the same |
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US8211820B2 (en) * | 2007-03-09 | 2012-07-03 | Kyoto University | Catalyst composition, and process for production of cross-coupling compound using the same |
JP2014024777A (en) * | 2012-07-25 | 2014-02-06 | Asahi Kasei Corp | Method for producing polycyclic aromatic compound having halogen atom |
CN103288583B (en) * | 2013-06-14 | 2016-03-23 | 中国科学院长春应用化学研究所 | A kind of 2,3, the preparation method of 3 ', 4 '-tetramethyl biphenyl |
CN106316745A (en) * | 2016-08-24 | 2017-01-11 | 苏州氟拓化工科技有限公司 | Preparing method of biphenyl compound |
CN108456172B (en) * | 2018-04-20 | 2021-01-12 | 浙江大学城市学院 | Chiral N-heterocyclic carbene precursor compound with benzimidazole skeleton and preparation method and application thereof |
JPWO2021106981A1 (en) * | 2019-11-27 | 2021-06-03 | ||
CN115093440B (en) * | 2022-08-29 | 2022-12-06 | 南昌大学 | Method for cross coupling of hydrosilane compound and azacyclo-aromatic compound |
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WO1997005151A1 (en) * | 1995-07-25 | 1997-02-13 | Clariant Gmbh | Catalyst for cross-coupling reactions |
DE19836470A1 (en) | 1998-08-12 | 2000-02-17 | Clariant Gmbh | Process for the preparation of 4-chlorobiphenyls |
JP4238405B2 (en) * | 1999-02-09 | 2009-03-18 | 東ソー株式会社 | Method for producing substituted styrene derivative or substituted biaryl derivative |
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JP4524506B2 (en) * | 1999-12-17 | 2010-08-18 | 東ソー株式会社 | Catalyst for cross-coupling reaction and method for producing aromatic allyl derivative using the same |
DE60219746T2 (en) * | 2001-11-19 | 2008-01-17 | Sumitomo Chemical Co., Ltd. | Process for the preparation of biaryl compounds |
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WO2009008447A1 (en) | 2009-01-15 |
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